CN105478107B - Application of the platinum catalyst in propane prepares propylene - Google Patents
Application of the platinum catalyst in propane prepares propylene Download PDFInfo
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- CN105478107B CN105478107B CN201510970983.6A CN201510970983A CN105478107B CN 105478107 B CN105478107 B CN 105478107B CN 201510970983 A CN201510970983 A CN 201510970983A CN 105478107 B CN105478107 B CN 105478107B
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- propylene
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 100
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000001294 propane Substances 0.000 title claims abstract description 75
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 70
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 27
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000004094 surface-active agent Chemical group 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910002846 Pt–Sn Inorganic materials 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 240000007591 Tilia tomentosa Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention discloses application of the platinum catalyst in propane prepares propylene, and the catalyst is with TiO2‑Al2O3Double oxide is carrier, and the active component of load is Pt, and Pt weight/mass percentage composition is 0.5 1.5%.TiO is prepared using sol-gal process2‑Al2O3Double oxide carrier, then obtained carrier impregnation is dried in platinum acid chloride solution, roasting, obtains Pt/TiO2‑Al2O3Catalyst.Catalyst of the present invention is applied to the preparing propylene by dehydrogenating propane faced under nitrogen atmosphere, TiO2Addition change product and reactant and the active force in activated centre, so as to improve Propylene Selectivity and carbon accumulation resisting ability, ensure that the catalyst has preferable reaction stability under the high temperature conditions.
Description
The present patent application is a kind of parent application " platinum catalyst for being carried on double oxide complex carrier and preparation method thereof
And application " divisional application, applying date of parent application is on July 14th, 2014, the Application No. of parent application
2014103338217。
Technical field
The present invention relates to a kind of loaded catalyst and its preparation method and application, is to be related to a kind of load specifically
In TiO2-Al2O3Pt catalyst on double oxide complex carrier and preparation method thereof and answering in preparing propylene by dehydrogenating propane
With.
Background technology
One of propylene is earliest adopted petrochemical materials, and produce important alkene of petrochemicals, it is main
It is used to produce polypropylene, acrylonitrile, expoxy propane, acrylic acid, methacrylaldehyde, the chemical products such as phenol and octyl alconyl.Current third
Alkene is mainly derived from the by-product of petroleum cracking ethene and petroleum catalytic cracking, due to by oil supply and product distribution etc. because
Element, traditional handicraft propylene can not meet the existing market demand.And in recent years, it is fast with China's oil chemical industry
Speed development, also increasingly increases the demand of propylene, and huge breach occurs in propylene market.Expand the production technology in propylene source
Mainly there is preparing propylene by dehydrogenating propane, alkene mutually converts, low-carbon hydrocarbon cracking and preparing propylene from methanol etc., wherein dehydrogenating propane system third
Alkene is of greatest concern and most promising approach.
Cheap propane feed can be converted into the alkene with high value by catalytic process and produced by dehydrogenating propane technique
Thing, product system is simple, and propene yield is high.Industrialized dehydrogenating propane technique has the Oleflex techniques of Uop Inc.,
The Catofin techniques of Lummus companies, the Star techniques and Linden techniques of Phillips techniques.Wherein, using most, scale
Maximum technique is Catofin techniques and Oleflex techniques.The catalyst that Catofin techniques use is chromium-based catalysts, but by
There is toxicity in chromium, be unfavorable for environmental protection, therefore its use is subject to certain restrictions.Oleflex techniques use platinum group
Catalyst, it has higher catalytic activity and Propylene Selectivity, environment-friendly, but platinum catalyst is expensive, reacts
Easy carbon distribution inactivation, stability are poor in journey.
The key of dehydrogenating propane technique is prepared with high activity, the catalyst of high stability.Dehydrogenating propane is catalyzed at present
Agent is mainly with Al2O3For carrier, using precious metals pt as active component, carbon distribution is reduced by adding auxiliary agent or changing support,
Improve stability.[the The effect of reaction conditions and time on such as Bengt Andersson
stream on the coke formed during propane dehydrogenation.Journal of Catalyst,
1996,164:44-53.] addition of Sn auxiliary agents is have studied to Pt/Al2O3The effect of catalyst.As a result show that Sn addition can be with
Promote Pt-Sn/Al2O3Catalyst surface carbon distribution is more deposited on carrier, protection activity center, so as to improve catalyst
Appearance charcoal amount.In Pt-Sn/Al2O3Alkaline assistant [Propane dehydrogenation over are added on the basis of catalyst
Pt-Sn/Rare-earth-doped Al2O3:Influence of La,Ce,or Y on the formation and
stability of Pt-Sn alloys.Catalysis Today,2011,164:214-220.], carrier surface can be neutralized
Part acid site, pressed down conversion of the unsaturated hydrocarbon molecule at support acidity center and the deposition in carrier surface before carbon deposit
System, so as to enhance carbon accumulation resisting ability, improves stability.It is stable to still need to further carry but the catalyst still inactivates quickly
It is high.[the Dehydrogenation of propane over Pt-SBA-15 and Pt-Sn- such as M.Santhosh Kumar
SBA-15:Effect of Sn on the dispersion of Pt and catalytic behavior.Catalysis
Today,2009,142:17-23.] it have studied a kind of effect using SBA-15 as the Pt series catalysts and Sn auxiliary agents of carrier.Knot
Fruit shows that the addition of Sn auxiliary agents improves the reactivity and Propylene Selectivity of catalyst, and relative to Al2O3Carrier, SBA-
Acidic site amount is less on 15 carriers, is advantageous to improve stability.But the conversion of propane of this catalyst is relatively low, still need into one
Step improves.
The content of the invention
The present invention is to solve existing platinum group catalyst carbon distribution is serious, easy in inactivation and selective low technical problem, carry
A kind of TiO is supplied2-Al2O3Double oxide carrier and support type Pt/TiO2-Al2O3The preparation method of catalyst and in dehydrogenating propane
In application, the problem of it is serious to overcome Pt series catalysts carbon distributions, and deactivation rate is fast and Propylene Selectivity is low, so as to improve third
Alkene yield.
In order to solve the above-mentioned technical problem, the present invention is achieved by following technical scheme：
A kind of platinum catalyst for being carried on double oxide complex carrier, the catalyst is with TiO2-Al2O3Composite oxides
For carrier, using Pt metal as activated centre；On the basis of catalyst gross mass, wherein Pt metal weight/mass percentage composition is 0.5-
1.5%, TiO2Weight/mass percentage composition is 5-20%.
Preferably, Pt metal weight/mass percentage composition is 1-1.5%, TiO2Weight/mass percentage composition is 10-15%.
Preferably, Pt metal exists in granular form in the catalyst, and the granular size of Pt metal is disperseed in 2-3nm
It is more uniform.
Above-mentioned catalyst is prepared as steps described below：
Step 1, by aluminium secondary butylate (ATSB), butyl titanate (TTB) and surfactant cetyl trimethylammonium bromide
(CTAB) it is dissolved in jointly in isopropanol, is sufficiently stirred to be well mixed, obtains mixed solution A；Wherein described aluminium secondary butylate dosage
For 7.5-9.5 mass parts, the butyl titanate dosage is 0.4-2 mass parts, the surfactant cetyl trimethyl
Ammonium bromide dosage is 0.7-0.8 mass parts, and the isopropanol dosage is 10-12 mass parts；Preferably, the aluminium secondary butylate is used
Measure as 7.7-9.2 mass parts, the butyl titanate dosage is 0.43-1.72 mass parts, the surfactant cetyl
Trimethylammonium bromide dosage is 0.75 mass parts, and the isopropanol dosage is 12 mass parts；
Step 2,65wt% concentrated nitric acid and deionized water are well mixed, obtain mixed solution B, then to mixed solution A
Middle dropwise addition mixed solution B is to be hydrolyzed, wherein the nitric acid that it is 65% that the concentrated nitric acid of the 65wt%, which is mass percent, is water-soluble
Liquid, dosage are 0.1-1.5 mass parts, preferably 0.1-1.41 mass parts；The deionized water dosage is 2.5-12.5 quality
Part, when being added dropwise, select to be added dropwise in 5-10min, hydrolysis temperature is 20-25 degrees Celsius of room temperature, hydrolysis time
At least 0.5h, preferably 1-2h；
Step 3, the reaction system obtained by step 2 is stood into 24-40h of aging under 20-25 degrees Celsius of room temperature, removed
After removing solvent, 20-24h is dried at a temperature of 70-90 DEG C, 3-5h is finally calcined at 550-650 DEG C, obtains TiO2-Al2O3It is multiple
Oxide is closed, as carrier；
Step 4, the TiO prepared by step 32-Al2O3Composite oxides are impregnated in the chlorine that concentration is 0.005-0.015g/mL
The platinic acid aqueous solution, so that Payload element platinum, wherein dip time at least 0.5h, preferably 1-2h；
Step 5, the TiO after step 4 is impregnated2-Al2O3Composite oxides dry 10-12h at a temperature of 80-100 DEG C,
3-5h is calcined at 550-650 DEG C again, finally in H2Fully reduced under atmosphere, obtain being carried on double oxide complex carrier
Platinum catalyst, i.e. Pt/TiO2-Al2O3Catalyst, it is preferred that in H21-3h is reduced under atmosphere.
Carry out facing propane under nitrogen atmosphere using above-mentioned catalyst and prepare propylene, carry out as steps described below：
Step 1, the catalyst of above-mentioned preparation is loaded into fixed bed reactors, nitrogen and hydrogen mixture is passed through, at 500-550 DEG C
At a temperature of carry out 1-2h of reduction to the catalyst, hydrogen volume ratio is 10-15% in nitrogen and hydrogen mixture；
Step 2, after the completion of to be restored, it is 550-650 DEG C to control reactor batch temperature, using propane mass space velocity as 3-
10h-1It is passed through reaction gas to be reacted, wherein propane and hydrogen mol ratio are 1:1, Balance Air is nitrogen.
During above-mentioned use, the catalyst of above-mentioned preparation is subjected to compressing tablet process, to obtain the graininess of 20-40 mesh
Catalyst is used.
Compared with prior art, technical scheme has the advantages that：
(1) catalyst of the invention is with TiO2-Al2O3Double oxide is carrier, has high-specific surface area and mesopore orbit,
Be advantageous to active component to be uniformly distributed and gas molecule diffusion；Using Pt as active component, using TiO2-Al2O3For carrier, TiO2
Addition change product and reactant and the active force in activated centre, so as to improve Propylene Selectivity and carbon accumulation resisting ability.
(2) catalyst of the invention is applied to face under nitrogen atmosphere, has good effect to preparing propylene by dehydrogenating propane, in height
Dehydrogenation activity is very high under the conditions of temperature, and Propylene Selectivity can reach 90%, and have good stability.
Brief description of the drawings
Fig. 1 is different TiO2The TiO of weight/mass percentage composition2-Al2O3The XRD spectra of carrier, wherein ▼ are Al2O3, ★ is
TiO2。
Fig. 2 is different TiO2The Pt/TiO of weight/mass percentage composition2-Al2O3The XRD spectra of catalyst, wherein ▼ are Al2O3,
★ is TiO2。
Fig. 3 is gained Pt and TiO2Weight/mass percentage composition is respectively 1.0% and 10% Pt/TiO2-Al2O3Catalyst
TEM schemes.
Embodiment
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) 8.7g aluminium secondary butylates (ATSB) are taken, 0.86g butyl titanates (TTB) and 0.75g CTAB are dissolved in 12g isopropyls jointly
In alcohol, rotor stirring 2h；
(2) take 65wt% concentrated nitric acid 0.705g and deionized water 12.5g to mix, it is molten that mixing is added dropwise into precursor solution
Liquid is hydrolyzed, hydrolysis time 0.5h；
(3) gel of generation is stood into aging 24h, then removes solvent, 20h is dried at a temperature of 70 DEG C, is calcined at 600 DEG C
3h, obtain TiO2-Al2O3Complex carrier；
(4) by TiO2-Al2O3Complex carrier is impregnated in the platinum acid chloride solution that concentration is 0.01g/mL, ultrasonic 0.5h, room temperature
Under the conditions of dry 12h；
12h is dried at a temperature of (5) 90 DEG C, is calcined 3h at 600 DEG C, that obtain is PtO2/TiO2-Al2O3Catalyst；Finally
In H21h is reduced under atmosphere, obtains Pt/TiO2-Al2O3Catalyst.
Obtained TiO2-Al2O3The XRD spectra of carrier is as shown in figure 1, Pt/TiO obtained by after reduction2-Al2O3Catalyst
(XRD uses Rigaku company Rigaku D/max-2500 shape diffractometers to XRD spectra, using Cu/K alpha rays as light as shown in Figure 2
Source is measured.Target is copper target, and 2 θ measurable angle ranges are 20~80 °, and sweep speed is 4 °/min, and test sample is after grinding
Powder, similarly hereinafter).Gained Pt/TiO after reduction2-Al2O3(TEM is public using JEOL as shown in Figure 3 for the TEM figures of catalyst
The JEM-2100F model Flied emissions transmission electron microscope of department).It can be seen that thus in the catalyst obtained by method Pt metal with
Particle form is present, and Pt granular size is disperseed more uniform in 2-3nm or so.
On the basis of catalyst gross mass, Pt weight/mass percentage composition is 1%, TiO2Weight/mass percentage composition be 10%.
(6) by Pt/TiO2-Al2O3Fine catalyst tabletting is the pellet type catalyst of 20-40 mesh；
(7) by the Pt/TiO after tabletting2-Al2O3Catalyst loads fixed bed reactors, nitrogen and hydrogen mixture is passed through, 500
To the catalyst prereduction 1h at a temperature of DEG C, hydrogen volume ratio is 10% in nitrogen and hydrogen mixture；
(8) it is 600 DEG C that reactor batch temperature is controlled after the completion of reducing, using propane mass space velocity as 10h-1It is passed through reaction
Gas, wherein propane and hydrogen mol ratio are 1:1, Balance Air is nitrogen.
Conversion of propane, Propylene Selectivity and propene yield various are calculated with following：
Conversion ratio：
Selectivity：
Yield：
Reaction product uses gas chromatograph on-line analysis, conversion of propane, Propylene Selectivity and propene yield and time
Relation it is as shown in table 1.
Table 1, the conversion of propane of differential responses time, Propylene Selectivity and propene yield
| Reaction time (h) | Conversion of propane (%) | Propylene Selectivity (%) | Propene yield (%) |
| 1 | 42.3 | 83.4 | 35.3 |
| 5 | 32.2 | 89.4 | 28.8 |
| 10 | 25.9 | 90.4 | 23.4 |
From table 1, the catalyst has higher activity and Propylene Selectivity, and embodies preferable stability.
Catalyst constantly inactivates, and is due to caused by carbon distribution caused by reaction.
Embodiment 2：
Reacted using the method for embodiment 1, it differs only in aluminium secondary butylate (ATSB) dosage in step (1) and is
9.2g, butyl titanate (TTB) dosage are 0.43g, TiO in gained catalyst2Weight/mass percentage composition is 5%.The TiO of gained2-
Al2O3The XRD spectra of carrier is as shown in figure 1, Pt/TiO obtained by after reduction2-Al2O3The XRD spectra of catalyst is as shown in Figure 2.
Embodiment 3：
Reacted using the method for embodiment 1, it differs only in aluminium secondary butylate (ATSB) dosage in step (1) and is
7.7g, butyl titanate (TTB) dosage are 1.72g, TiO in gained catalyst2Weight/mass percentage composition is 20%.Obtained TiO2-
Al2O3The XRD spectra of carrier is as shown in figure 1, Pt/TiO obtained by after reduction2-Al2O3The XRD spectra of catalyst is as shown in Figure 2.
It will be seen from figure 1 that the composition of obtained carrier is TiO2And Al2O3, it is verified as double oxide complex carrier；When
TiO2When percentage composition is 5%, no TiO2Peak occurs, and works as TiO2When weight/mass percentage composition reaches 10%, there is TiO2Diffraction maximum and
Its peak intensity is with TiO2Weight/mass percentage composition increase and constantly strengthen, and Al2O3Peak intensity constantly weaken therewith, thus prove
TiO2It is distributed in Al2O3Surface, and high degree of dispersion.
It can be seen from Fig. 2 that Pt addition does not have an impact TiO2-Al2O3The structure and TiO of carrier2In Al2O3Point on surface
Dissipate；And Pt diffraction maximum is not detected in spectrogram, it was demonstrated that Pt particle heights are dispersed in carrier surface.
Embodiment 4：
Reacted using the method for embodiment 1, it is 0g that it, which differs only in the concentrated nitric acid dosage of step (2),.
Embodiment 5：
Reacted using the method for embodiment 1, it is 1.41g that it, which differs only in the concentrated nitric acid dosage of step (2),.
Embodiment 6：
Reacted using the method for embodiment 1, it is 2.5g that it, which differs only in the deionized water dosage of step (2),.
Embodiment 7：
Reacted using the method for embodiment 1, it is 7.5g that it, which differs only in the deionized water dosage of step (2),.
Embodiment 8：
Reacted using the method for embodiment 1, it differs only in the drying temperature of step (3) as 80 DEG C.
Embodiment 9：
Reacted using the method for embodiment 1, it differs only in the drying temperature of step (3) as 90 DEG C.
Embodiment 10：
Reacted using the method for embodiment 2, it is 550 that it, which differs only in step (3) and the sintering temperature of step (5),
℃。
Embodiment 11：
Reacted using the method for embodiment 3, it is 650 that it, which differs only in step (3) and the sintering temperature of step (5),
℃。
Embodiment 12：
To be reacted using the method for embodiment 4, its chloroplatinic acid concentration differed only in step (4) is 0.005g/mL,
Pt weight/mass percentage compositions are 0.5% in obtained catalyst.
Embodiment 13：
To be reacted using the method for embodiment 1, its chloroplatinic acid concentration differed only in step (4) is 0.015g/mL,
Pt weight/mass percentage compositions are 1.5% in obtained catalyst.
Embodiment 14：
Reacted using the method for embodiment 1, it differs only in the drying temperature of step (5) as 80 DEG C.
Embodiment 15：
Reacted using the method for embodiment 1, it differs only in the drying temperature of step (5) as 100 DEG C.
Embodiment 16：
Reacted using the method for embodiment 1, it differs only in the reaction temperature of step (8) as 550 DEG C.
Embodiment 17：
Reacted using the method for embodiment 1, it differs only in the reaction temperature of step (8) as 650 DEG C.
Embodiment 18：
Reacted using the method for embodiment 1, it is 3h that it, which differs only in the propane mass space velocity of step (8),-1。
Embodiment 19：
Reacted using the method for embodiment 1, it is 7h that it, which differs only in the propane mass space velocity of step (8),-1。
On above-described embodiment result and data, contrasted using the activity data of 5h after reaction, to investigate different ginsengs
Several influences to catalyst reaction performance.
(1) TiO2Influence of the weight/mass percentage composition to catalyst reaction activity, referring to table 2.Reaction condition with embodiment 1,
2、3。
Table 2, TiO2Influence of the weight/mass percentage composition to catalyst reaction activity and Propylene Selectivity
| TiO2Weight/mass percentage composition (%) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 5 | 28.7 | 88.3 | 25.3 |
| 10 | 32.2 | 89.4 | 28.8 |
| 20 | 25.6 | 92.7 | 23.7 |
From result above it can be seen that, with TiO2Content increase, the selectivity of propylene is continuously increased, but propane turns
Rate occurs first increasing the trend reduced afterwards, and the yield of propylene also occurs first rising the rule declined afterwards.It can be seen that TiO2Matter
When amount content is 10%, conversion of propane 32.2%, Propylene Selectivity 89.4%.Propene yield reaches 28.8%, reaches
Optimal value.
(2) influence of the Pt weight/mass percentage composition to catalyst reaction activity, referring to table 3.Reaction condition with embodiment 1,
12、13。
The influence of table 3, Pt weight/mass percentage composition to catalyst reaction activity and Propylene Selectivity
| Pt weight/mass percentage compositions (%) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 0.5 | 25.6 | 91.3 | 23.4 |
| 1.0 | 32.2 | 89.4 | 28.8 |
| 1.5 | 33.1 | 85.5 | 28.3 |
As can be seen from the above results, as the increase of Pt contents, conversion of propane gradually increase, but when Pt contents by
1.0% when increasing to 1.5%, conversion ratio increase unobvious, starts to tend towards stability；And the increase of Pt contents causes Propylene Selectivity
Constantly lower, propene yield occurs first increasing the trend reduced afterwards.When Pt weight/mass percentage compositions are 1.0%, propene yield is optimal.
(3) TiO2-Al2O3Influence of the concentrated nitric acid dosage to catalyst reaction activity and Propylene Selectivity in preparation process,
Referring to table 4.Reaction condition is the same as embodiment 1,4,5.
Table 4, TiO2-Al2O3Influence of the concentrated nitric acid dosage to catalyst reaction activity and Propylene Selectivity in preparation process
| Concentrated nitric acid dosage (g) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 0 | 30.4 | 87.3 | 26.5 |
| 0.705 | 32.2 | 89.4 | 28.8 |
| 1.41 | 31.0 | 89.8 | 27.8 |
It is can be seen that from the result in table as the increase of concentrated nitric acid dosage, Propylene Selectivity gradually increase, but work as dense nitre
When sour dosage increases to 1.41g by 0.705g, selectivity increases unobvious, starts to tend towards stability；And the increase of concentrated nitric acid dosage
Conversion of propane is first increased reduces afterwards, declines afterwards so as to promote propene yield first to rise.Therefore optimal concentrated nitric acid dosage be than
For 0.705g.
(4) TiO2-Al2O3The dosage of deionized water is to catalyst reaction activity and the shadow of Propylene Selectivity in preparation process
Ring, referring to table 5.Reaction condition is the same as embodiment 1,6,7.
Table 5, TiO2-Al2O3The dosage of deionized water is to catalyst reaction activity and the shadow of Propylene Selectivity in preparation process
Ring
| Deionized water dosage (g) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 2.5 | 27.8 | 90.3 | 25.1 |
| 7.5 | 29.6 | 91.5 | 27.1 |
| 12.5 | 32.2 | 89.4 | 28.8 |
It is can be seen that from the result in table as the increase of deionized water dosage, conversion of propane are continuously increased, and propylene selects
Selecting property first increases to be reduced afterwards, but change is faint, and propene yield constantly raises with the increase of water consumption.
(5) TiO2-Al2O3Drying temperature (step 3) is to catalyst reaction activity and Propylene Selectivity in preparation process
Influence, referring to table 6.Reaction condition is the same as embodiment 1,8,9.
Table 6, TiO2-Al2O3Influence of the drying temperature to catalyst reaction activity and Propylene Selectivity in preparation process
The rise with drying temperature is can be seen that from the result in above-mentioned table, conversion of propane constantly reduces, and propylene
Selectivity change is very little, and propene yield constantly reduces with the rise of drying temperature.Therefore, in carrier preparation process most
Good drying temperature is 70 DEG C.
(6) influence of the sintering temperature to catalyst reaction activity and Propylene Selectivity in carrier and catalyst preparation process,
Referring to table 7.Reaction condition is the same as embodiment 1,10,11.
Influence of the sintering temperature to catalyst reaction activity and Propylene Selectivity in table 7, carrier and catalyst preparation process
| Sintering temperature (DEG C) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 550 | 30.1 | 90.6 | 27.3 |
| 600 | 32.2 | 89.4 | 28.8 |
| 650 | 27.8 | 91.3 | 25.4 |
The rise with sintering temperature is can be seen that from the result in table, conversion of propane is first raised and reduced afterwards, and propylene
Selective changing rule is on the contrary, first reduce increases afterwards, and propene yield is presented first to raise with the rise of sintering temperature and dropped afterwards
Low trend.Therefore, optimum calcination temperature is 600 DEG C.
(7) in catalyst preparation process (step 5) drying temperature to catalyst reaction activity and Propylene Selectivity shadow
Ring, referring to table 8.Reaction condition is the same as embodiment 1,14,15.
Influence of the drying temperature to catalyst reaction activity and Propylene Selectivity in table 8, catalyst preparation process
| Drying temperature (DEG C) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 80 | 32.7 | 86.5 | 28.3 |
| 90 | 32.2 | 89.4 | 28.8 |
| 100 | 30.5 | 91.3 | 27.8 |
The rise with drying temperature is can be seen that from the result in above-mentioned table, conversion of propane constantly reduces, and propylene
Selectivity is gradually increasing, and propene yield constantly reduces with the rise of drying temperature.Therefore, it is optimal in catalyst preparation process
Drying temperature is 90 DEG C.
(8) influence of the reaction temperature to catalyst reaction activity and Propylene Selectivity, referring to table 9.Reaction condition is the same as implementation
Example 1,16,17.
The influence of table 9, reaction temperature to catalyst reaction activity and Propylene Selectivity
| Drying temperature (DEG C) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 550 | 19.8 | 94.3 | 18.7 |
| 600 | 32.2 | 89.4 | 28.8 |
| 650 | 42.7 | 56.8 | 24.3 |
From the results, it was seen that because dehydrogenating propane is the endothermic reaction, with the rise of reaction temperature, conversion of propane is not
Disconnected rise, but Propylene Selectivity but drastically declines, propene yield then reduces as the rise of reaction temperature first increases.Cause
This, dehydrogenating propane optimal reaction temperature is 600 DEG C.
(9) influence of the propane mass space velocity to catalyst reaction activity and Propylene Selectivity, referring to table 10.Reaction condition
With embodiment 1,18,19.
The influence of table 10, propane mass space velocity to catalyst reaction activity and Propylene Selectivity
| Propane mass space velocity (h-1) | Conversion of propane (%) | Propylene Selectivity (%) | Propane recovering rate (%) |
| 3 | 36.3 | 76.8 | 27.9 |
| 7 | 34.5 | 81.4 | 28.1 |
| 10 | 32.2 | 89.4 | 28.8 |
As can be seen from the above results, as the rise of propane mass space velocity, conversion of propane constantly reduce, propylene selection
Property then raises, and propene yield also constantly rises.Optimal propane mass space velocity is 10h-1。
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (9)
1. application of the platinum catalyst in propane prepares propylene, it is characterised in that the platinum catalyst is with TiO2-Al2O3Composite oxygen
Compound is carrier, using Pt metal as activated centre；On the basis of catalyst gross mass, Pt metal is with granulated in the catalyst
Formula is present, and the granular size of Pt metal is uniformly dispersed in 2-3nm, and wherein Pt metal weight/mass percentage composition is 0.5-1.5%,
TiO2Weight/mass percentage composition is 5-20%, and is prepared as steps described below：
Step 1, aluminium secondary butylate, butyl titanate and surfactant cetyl trimethylammonium bromide are dissolved in isopropanol jointly
In, it is sufficiently stirred to be well mixed, obtains mixed solution A；Wherein described aluminium secondary butylate dosage is 7.5-9.5 mass parts, described
Butyl titanate dosage is 0.4-2 mass parts, and the surfactant cetyl trimethylammonium bromide dosage is 0.7-0.8 matter
Part is measured, the isopropanol dosage is 10-12 mass parts；
Step 2,65wt% concentrated nitric acid and deionized water are well mixed, obtain mixed solution B, then drip into mixed solution A
Add mixed solution B to be hydrolyzed, wherein the aqueous solution of nitric acid that it is 65% that the concentrated nitric acid of the 65wt%, which is mass percent, is used
Measure as 0.1-1.5 mass parts；The deionized water dosage is 2.5-12.5 mass parts, when being added dropwise, select 5-
It is added dropwise in 10min, hydrolysis temperature is 20-25 degrees Celsius of room temperature, hydrolysis time at least 0.5h；
Step 3, the reaction system obtained by step 2 is stood into 24-40h of aging under 20-25 degrees Celsius of room temperature, removed molten
After agent, 20-24h is dried at a temperature of 70-90 DEG C, 3-5h is finally calcined at 550-650 DEG C, obtains TiO2-Al2O3Composite oxygen
Compound, as carrier；
Step 4, the TiO prepared by step 32-Al2O3Composite oxides are impregnated in the chloroplatinic acid that concentration is 0.005-0.015g/mL
The aqueous solution, so that Payload element platinum, wherein dip time at least 0.5h；
Step 5, the TiO after step 4 is impregnated2-Al2O3Composite oxides dry 10-12h at a temperature of 80-100 DEG C, then
3-5h is calcined at 550-650 DEG C, finally in H2Fully reduced under atmosphere, the platinum for obtaining being carried on double oxide complex carrier is urged
Agent, i.e. Pt/TiO2-Al2O3Catalyst.
2. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that facing nitrogen atmosphere
Under propylene prepared with propane, carry out as steps described below：
Step 1, the platinum catalyst for being carried on double oxide complex carrier is loaded into fixed bed reactors, is passed through nitrogen and hydrogen mixture,
1-2h of reduction is carried out to the catalyst at a temperature of 500-550 DEG C, hydrogen volume ratio is 10-15% in nitrogen and hydrogen mixture；
Step 2, after the completion of to be restored, it is 550-650 DEG C to control reactor batch temperature, using propane mass space velocity as 3-10h-1It is logical
Enter reaction gas to be reacted, wherein propane and hydrogen mol ratio are 1:1, Balance Air is nitrogen.
3. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that enter catalyst
Row compressing tablet process, used with obtaining the pellet type catalyst of 20-40 mesh.
4. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that Pt metal quality
Percentage composition is 1-1.5%.
5. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that TiO2Quality hundred
It is 10-15% to divide content.
6. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that in step 1,
The aluminium secondary butylate dosage is 7.7-9.2 mass parts, and the butyl titanate dosage is 0.43-1.72 mass parts, the surface
Lammonium bromide dosage is 0.75 mass parts, and the isopropanol dosage is 12 mass parts.
7. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that in step 2,
The concentrated nitric acid dosage of the 65wt% is 0.1-1.41 mass parts；1-2h of hydrolysis time.
8. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that in step 4,
1-2h of dip time.
9. application of the platinum catalyst according to claim 1 in propane prepares propylene, it is characterised in that in steps of 5,
In H21-3h is reduced under atmosphere.
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| CN104971717B (en) * | 2015-06-25 | 2017-09-22 | 天津大学 | The ZnO/Al of Pt modifications2O3Catalyst and its preparation method and application |
| CN108722469B (en) * | 2017-04-22 | 2021-11-05 | 天津大学 | Supported high-selectivity core-shell structure bimetallic catalyst and preparation method and application thereof |
| CN109718801B (en) * | 2017-10-27 | 2022-02-15 | 万华化学集团股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN110270367B (en) * | 2018-03-16 | 2022-04-08 | 天津大学 | In-situ packaged noble metal Pd molecular sieve catalyst and preparation method and application thereof |
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| CN109289831A (en) * | 2018-10-09 | 2019-02-01 | 天津科技大学 | The catalyst of preparing propylene by dehydrogenating propane and preparation method thereof with high anti-carbon |
| CN111135811B (en) * | 2018-11-05 | 2021-02-05 | 中国石油大学(北京) | Catalyst for dehydrogenation of low-carbon alkane and application thereof |
| CN111229222A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Platinum catalyst for catalyzing low-temperature alkane oxidation and preparation and application thereof |
| CN114054021B (en) * | 2020-07-31 | 2023-05-12 | 中国科学院大连化学物理研究所 | Application of Cu catalyst in alkane dehydrogenation reaction |
| CN114471726B (en) * | 2022-01-26 | 2023-12-29 | 淮安晨化新材料有限公司 | Preparation method and application of efficient catalyst for hydrosilylation reaction |
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| CN115779894A (en) * | 2022-12-27 | 2023-03-14 | 黄河三角洲京博化工研究院有限公司 | Pt-based catalyst taking bimetallic oxide as carrier, preparation method and application |
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